Azo compounds



Patented 12, 1938 PATENT OFF-ICE 2.123.034 Azocom'omms mu Mictuch and Jose! Klarer, Wuppertal- Elberleld,

Germany, assignors to Winthrop,

Chemical Company, Inc., New York, N. Y., a corporation or New York No Drawing. Application January 29, 1937', Se-

m1 No. 122,981. 'ln Germany April 18,1934

This invention relates to'azo compounds which display a bactericidal action, and to a process of preparing-the same.

U. 5. Patent No. 2,085,037, June-29, 1937, re-

5. fers to the manufacture of ass compounds displaying a bactericidal action, which azo compounds have the general formula:

' R rl=N--R 10 wherein R stands for a para-sultamide or disultamide'substituted radical of the benzene series and RF stands for a cyclic radical containing nitrogen in basic linkage, that is for an aminobenzene or aminonaphthalene radical which 15 contains at least one further basic nitrogen atom in the form of an amino or alkylamino group. Acid groups should not be present in the said azo compounds since it has been found'that the bactericidal activity of the azo compounds speck 20 fled is reduced to a far-reaching extent by the presence of acid groups. For instance, the 2,4- diaminoazobenzene-d sulfonic -acid ide becomes inactive by the introduction a carboxylic acid groupin the 2'-position. This bhaviour of the said can compounds was disadvantageous in so far as a greater solubility of the said azo compounds was desired for their parenteral administration, whereas the introduction 01 acid groups is known as a medium which 0 is suitable to effect a greater solubility of a chemical compound. For. the above-mentioned.

= reason first itappeared necessaryin-the present case to take other ways in order to effect an increase of the solubility ofthe azo compounds 35 specified above; .However, we have made the surprising discovery that the introduction. of acid groups into the azo compounds mentloned does not in every case reduce their bac- 45 gen atoms, but only this radical," may also con-- tain a hydrosyl group instead of one basic nitrogen atom. Regarding the activity and solubility it is immaterial 'whether the. free acid group is present in the form of" nucleo-bound sulionic o.or carboxylic groups, or whether these groups are bound by means of intermediate members,

for instance, aminomethanesultonic acid, amino.- acetic, hydroxy acetic, aminoethane sulionic acid and other radicals may be introduced to elect 55 an increased solubility; The. amino or hydroxyl groups which are characteristic substituents of the one radical attached to the azogroup may serve as intermediate members. Accordingly, new'products which display a considerable bac-i tericidal activity and a good solubility in water 5 are obtainable by the .manufactureof azo compounds of the formula:

I wherein It stands for a cyclic radical selected from the group consisting of para-sulfamide and disulf amide substituted radicals of. the benzene series, in which radical the amino group of the sulfamide groups may be substituted by alkyl groups or an alkylene group, and wherein It stands for a cyclic radical containing nitrogen selected from the -group consisting of aminobenzene and aminonaphthalene radicals, which radicals contain at least one further basic nitrogen atomin the form of an aminoor alkyl- 0 amino group or contain at 'least one hydroxyl group and further contain at least one acid group which may be a substituent of the amino or hydroxyl group. In these compounds the amido group attached to the sulfonic acid group(s) maybea primary, secondary or tertiary amido group. It may be substituted by alkyl groups, such. as methyl, ethyl, propyl and butyl, or by. an alkylene group, such as the tetramethylene and pentamethylene group, in which case the amido group forms a pyrrolidyl or piperidyl nucleus. However, it may be expressly stated that hydroxyalkyl groups should not be present since they strongly reduce the bactericidal activity contrary to the other substituents. The benzene radical bearing the sulfonic acid amide group(s) may contain further substituents, for instance, alkyl groups, such as methyl and ethyl, but free acid groups should not be present in this radical.

The amino group which is present in the other radical attached to the azo group may be substituted by alkyl groups, such as methyl, ethyl and butyl groups, by acyl groups, such as the acetyl, benzoyl, amino acetyl, amino benzoyl, carbamic acid, the guanyl and biguanyl radical without the bactericidal activity of the am compounds being substantially aflfected. correspondingly, the term amino when used in the appended claims is intended to include. also such subab' tuted amino groups. The amino group mayalso 5o be usedas a member to connect two molecules of the sac compounds specified by means 01' the carbonyl or, carbimido group, so that a urealike or guanidine-like linkage is produced.

The tree acid group which is preferably a sulionic acid or carboxyiic acid group may be present once or several'times. In view, of the presence oi the acid groups the new ar'o compounds are capable of forming salts with bases, such as the alkali and alkaline-earth metal bases, for instance, v calcium-, strontium-, sodium-. potassiumand lithium-hydroxide or carbonate. or with ammonia or amine bases, such as diethylamine, dihydroxyethyiamine, ethylenediamine. -diethylarninoethanol, pip rldine and piperaaine.

In accordance with the present invention the new aao compounds speciiied above are obtainable by reacting upona-cyclic nitrogenous compound selected i'rom the group consisting oi aminobenzene and aminonaphthalene compounds which contain at least one further nitrogen atom in the form oi an amino. or aikylamino group or at least one hydroxyl group, and further contain at least one acid group which maybe a substituent of the amino or hydroxyl sroup. with a diazo compound selected from the group consisting of para-suliamide and 'disuliamide substituted diare compounds of the benzene series in which theaminogroupoithemliamidegroupmaybe substituted by alkyl groups or by an alhylene group. The reaction is advantaaeously carried out in the presence oi water at a low temperature. say at about .C. or below.

The aao compounds thus obtainable are colored powderswhlchinthe iormoitheiralkali or al kaline-earth metal, ammonium or amine salts' ingeneralare solubleinwater. Inviewoitheir considerable bactericidal activity they. have proved active in the treatment. oi infectious di- 'lhe invention is further illustrated by the follgwing examples without being restricted there- Imple 1.-20.8 of hydrochloride ot 4-aminobenzenesulionic acid amide are dissolved in, 100 ccs. oi water and aiter the addition or 15 cos. of concentrated hydrochloric acid diaaotised with a solution oi! 6.9 grams oi sodium "nitrite inwater. A'solution 0! 18.8 grams of 1,3- phenylenediamine-i-suli'onic acid with grams of sodium acetate dissolved in water is added to this dlaso solution. The 2.4-diaminoasobensene- S-suli'onic acid-4'-sulionic acid amide precipitates immediately as a brownish red precipitate.

'It is suched'oi! and obtained from water in the tom of brown needles which are readily soluble in alkalies with a yellowish red coloration.-

By heating the tree sultonic acid with excess ammonia 'or dlethyiamineand by theaddition oiether the ammonium, the diethylamine salt respectively, are obtained. The yellow red'salts arereadilysolubleinwater. Byheatingtheireesuli'onic acid with ethylene diamine and distilling oi! the excess ethylene diamine in vacuo' the ethylene diamine salt is obtained in the form of an orange red, powder which is readily soluble in water. -By heating the free, acid with piperazine and by the addition oi acetone the orange red readily soluble piperaaine saltis obtime By heating the tree acid with one equiv-. alent o! diethanolamine the diethanolamine salt is obtained.

Iaample 2.40.8 grams of the hydrochloride magnesium-,

of i-aminobenzene sul ionic acid amide are diazotized as indicated in Example 1 and treated with an alkaline solution of 18.9 grams of 3- aminophenol-6-sulfonic acid. -The azo compound is obtained as -a brown precipitate from the yellowish red solution by means'oi dilute hydrochloric acid. The precipitate is dissolved in dilute sodiumfcarbonate solution while gently heating. By the addition oi acetic acid and s0- dium chloride solution the 2-amino-4-hydroxyl- It is readily soluble in" water with an olive green coloration, in sodium carbonate solution with an orange yellow coloration. .The azo compound is precipitated by means oi'hydrochloric acid.

In this example the 3-aminophenol-6-sulfonic' acid may be replaced by 23.1 grams of 3-acetylaminophenol-ii-sulfonic acid. Thus the 2-acetylamino-4-hydroxyazobenzene-5-sulionic acid 4'- sulfonic acid amide is obtained as a water-soluble yellow red powder; or the 3-aminophenol- B-sulfonic acid may be replaced by 20.2 grams oi the symmetric urea compound from 3-aminophenol-6-sulionic acid. A brownish yellow azo compound which is soluble in water with a brownish yellow and in dilute caustic soda solution with an orange coloration is thus obtained azobenzene-S-sulionic acid-4'-sultonic acid amide is precipitated as an olive green colored powder.

which'is precipitated by excess caustic soda solution in the form of the. sodium salt. It has the formula:

Further, the S-aminophenol-G-sulfonic acid may be replaced by 22.3 grams of symmetric 'guanide oi the 3-aminophenol-6-sulionic acid. Thus a brown azo compound is obtained which is soluble in water with a yellowish brown, in

- caustic soda solution with a yellowish red colm'ation; the product corresponds to the aforementioned formula, but instead 0! the CO= group stands the =C=NH group.

. "'1he3-aminophenol-6-sulionic acid may also be replaced by 23.5 grams or the condensation product from 1 mol. of cyanuric chloride, 2 mols oi 3-aminophenol-6-sulionic acid and 1 mol. of ammonia (a white readily soluble powder in dilute alkalies). A yellow brown azo compound 1 which can be precipitated from an aqueous solu- Nil- Emmple 3.-1'l.2 grams or i-aminobenzenesulionic acid amide are dissolved in 25 cos. oi. concentrated hydrochloric 'acid 'and water and dialotizedwith 6.9 grams, of sodiumnitrite. Thediam solution is added to a solution oi 18.8 grams of S-a'minophenylglycine in sodium acetate solution, whereupon the dyestui! first precipitates in an oily form but solidifies to crystals on the addition pot ice water. The 4'-sulfonic acid amide-phenylazo-3-amidophenylglycine obtained in this manner is dissolved in sodium bicarbonate for purification and reprecipitated with dilute acetic acid. The red-brown crystal powder melts at 189 C. and dissolves in caustic soda solution and sodium carbonate solution with red-brown coloration.

Example 4.20.8 grams of the hydrochloride oi! 4-aminobenzenesulionic acid amide are diazotized as specified above and coupled with 28.2 grams oi. the sodium salt oi 2-amino-5-naphthol- 'I-sulionic acid in alkaline solution. 'Ihe 2-amino-5-naphthol-7-sulionic acidphenyl-4-sul-. tonic acid amide is obtained as a ed brown precipltate from the dark red solution by the addition of hydrochloric acid. The precipitate is dissolved in dilute sodium carbonate solution and separatedagain by means oi hydrochloric acid. The compound is readily soluble inalkalies with a red coloration. v

The sodium salt 0! 2-amino-5-naphthol-7-sulionic acid may be replaced by 28.2 grams '0! 2 acetylamino 5 naphthol-l-sulionic acid.

Thus a brown red azo compound is obtained which is soluble in water with a yellow red. in alkalies with. a cherry red coloration; or by 35.8 grams of 2- (m 'aminobenzoyl amino) -5- naphthol-l-sulionic acid. Thus a 'red brown azo compound is obtained which is soluble in alkalies with a dark red coloration; or by 28.3 grams of 2-ureido-5-naphthol-7-sulionic acid. Thus. a

brick red azo compound is obtained'which is solu-.

ble in water with a yellow red, in caustic soda solution with a red coloration; or by 32.4 grams of 2-biguanide-5-naphthol-i-sulionic acid. A

brown red azo compound is obtained which is soluble in alkalles with a red coloration: :iromthis solution the sodium salt may be obtained as red brown precipitate which is readily soluble in water by means of sodium chloride or acetone;

or by 29.6 grams of 2-glycinamide-5-naphtholr7- sulfonic acid. A brown azo compound which is soluble in acetic acid with a-brown, and in dilute caustic soda solutionwith a red coloration is thus obtained; or by 25.3 grams of 2-methylamino-5- naphthol-l-sulfonic acid. A red brown azo compound which is readily soluble in water with the same coloration is thus obtained. By means of .caustic soda solution-the. color turns to red. The compound is soluble in methyl alcohol; or by 29.5 grams of 2-diethylamino-5-naphthol 'l sultonic acid. A green brown azo compound which isreadily soluble in water and methyl alcohol with a red brown coloration is thus obtained. The aqueous solution is colored carmine red by means of caustic soda solution; or by 23 grams of 5.5'-dihydroxy- 1 2.2'- dinaphthylamine-'l.'idisulfonic acid. A

. black brown aso compound is thus obtained. The solution in water takes a cherry red coloration,

in-caustic soda solution acarmine red coloration;

a5-or by 25.2 grams oi the symmetric urea'compound oi the 2-amino-5-naphthol-7-sulionic acid. Thus a brown azo compound is obtained which is soluble in sodium carbonate solution with a brown red coloration. From this solution the sodium .salt. may be precipitated as brown red precipitate bymeans of alcohol: or by 28 grams oi symmetric thiourea oi the 2-aminc-5-naphthol-7-sulionic acid. Thus'a brown red compound is obtained which is soluble in alkalies with a blood red color ation; or by 25.1 grams or symmetric guanide or the 2-amino-5-naphthol-7-sulionic acid. A red brown aso compound is obtained which is soluble as sodium salt with a yellow red coloration and which can be precipitated by means of sodium chloride; or by 23.9 grams oi 2-amino-8 hydroxynaphthalene-d-suli'onic acid. A dark brown azo compound which is soluble in caustic soda solution with a deep red coloration is'thus obtained;- or by 28.2 grams of 2-acetylamino-8- I hydroxynaphthalene-G-suli'onic acid. Thus a red brown aao compound is obtained which is soluble in acid solution with a yellow red coloration,

in caustic soda solution witha dark redcoloration: or by 38.1 grams oi 2-acetylamino-8-naphthol-3,6-disulioni'c acid. Thus ared brown aso compound is obtained which is soluble in acid solution with a red. and in caustic soda solution with a brown red coloration: or by 42.3 grams of 1-benzoylamino-8-naphthol-4,8-disulionic acid. A red brown azo compound is thus obtained which is soluble in acid solution with rhodamin red. and in caustic alkali solution witha yellow red coloration: or by 32.8 grams of 1,8-perimidine-8,8-disulionlc acid oi the formula:

; noisf son! A violet red m compound is obtained which is soluble in dilute mineral acid with weak brown, in caustic soda solution with strong blue colora tion: or by 37.2 grams of 4'-aminophenyl-5-hydroxynaphtho-l.2-thiaaole 7-sultonic acid oi the formula:

a" black brown azo compound is obtained which is soluble in caustic soda solution with a carmine I red. coloration; or by 34.8 grams of the conden sation product from one mol. ot'cyanuric chloride, 1 mol. of 2-amino-5-naphthol-7-sulfonic acid and 2 mols or ammonia. .A'red brown aao- -compound is thus obtained which-is soluble in sodium carbonate with an orange, and in'caustic solution-with blood red coloration. Example 5.--29.1 grams of 2.4-diaminoa'sobenz'cne-4'-sulfonic acidamide are suspended in- It is decomposed by means of hydrochloric acid while evolving sulfur dioxide and separating the original azo compound.

, In the same manner 29.2 grams of 2-amino-4- hydroxyazobenzene-4'-sulfonic acid amide meltns at 106 C. are treated. The sodium salt of By the addition of hydrochloric acid and the 2-amino-4-hydroxyaaobenzene-N-methanesulionic acid-4'-sulionic acid amide is obtained as a light brown powder which is readily soluble in water. It is decomposed with hydrochloric acid.

Example 6.--l1.2 grams or i-aminobenzenesulionic acid-amide are dissolved in cos. of concentrated hydrochloric acid while adding water and diazotized with a solution of 6.9 grams of sodium nitritein water. The diazo solution is added drop by drop to a solution or 20.3 grams 0! 6-amino-2-hydroxy-3-naphthoic acid in 400 ccs. oi 10% sodium carbonate solution andthe aao compound iormed salted out after stirring for one hour and adding 150 grams of sodium chloride. The separated brown violet dyestufl is' filtered with suction, washed with sodium chloride solution, dissolved in warm water and again salted out. From the aqueous solution of the dyestuil purified in this manner the free 4'-sulionic acid amide-phenylazo 6-amino-2-hydroxy- S-naphthoic acid separates as a brown violet precipitate with 10% acetic acid. It dissolves in dilute caustic soda solution with pure violet, in sodium carbonate solution with brown violet coloration. In acetic acid it is only slightly soluble when cold, on heating it dissolves with a brown coloration. Concentrated hydrochloric acid takes up the dyestui! with violet red, con-, centrated sulfuric acid with brownish red color-.

ation.

Example 7.30.7 grams of l-aminobenzene- 3,5-di-(suli'onic acid dimethylamide) melting at 182 0., in 150 cos. of acetic acid, cos. of water and 25 cos. of concentrated hydrochloric acid are diazotized with a solution of 6.9 grams of sodium nitrite in water. The diazo solution is added to a strongly soda alkaline solution of 36.1 grams of 1 acetylamino 8 -naphthol 3,6 9 disulfonic acid.

Alter prolonged stirring the solution is acidified ;with acetic acid, precipitated with sodium chloride and filtered with suction. The azo compound which is recrystallized from methanol is .a dark brown powder which is soluble indilute hydrochloric acid with yellow red, in caustic soda solution with violet red coloration.

E trample 8.Through the heated'solution of 2-amim-4 -hydroxy hydrasobenzene 5 sulionic acid-4'-sulionic acidamide acidified with dilute acetic acid a current of air is passed until the first colorless solution shows a strongly olivecoloration and no further deepening of the color sodium chloride the 2-amino-4-hydroxyazoben- 'sene-t-sulfonic acid-4'-sulronic acid amide is obtained as anollvrgreen colored powder which is readily soluble in water with anlolive green,

in sodium carbonate solution with orange yellow coloration.

Example 9.40.8 grams of the hydrochloride of the i-aminobensenesuli'onic acid amide are diasotimdin the manner above specified and l-treated with a soda alkaline solution 0116.9

grams or 8-nitro-2-naphthol-8-sulionic acid (compare Annalen 323 (l902),page 122). From the intensely brown red solution the aao compound is precipitated by means of dilute hydrochlorieacid. It is purified by redissolving from sodium carbonate solution and by precipitation withhydrochloric acid. After filtering with suction and washing with sodiumchloride solution 50 grams ofthe 6-nitro-2-naphthol-8-sulionic acid-azophenyl-f-sulionlc acid amide are dissolved in 300 cos. of alcohol and 150 cos; of 20% aqueous ammonia. Into this solution which is heated on the water bath while stirring a concentrated aqueous solution of 200 grams oi-ierrous sulfate are introduced. Thereby the color of the reaction liquid becomes darker. At about 45 minutes the reaction mixture is oil. from the iron sludge. After cooling the 6- amino-li-naphthol-ii-sulionlc acid-asopbcnyl-4'- sulionic acid amide is obtained as a red brown precipitate by means of hydrochloric acid.

Example 1042.7 grams or the hydrochloride of the 4-aminobenzene-sultonic acid chloride are 'diazotized with 7 grams of sodium nitritewhile cooling well and treated with a hydrochloric acid solution or 29.5 grams of 2-diethylamino-5- naphthbl-l-sulionic' acid. By the addition oi sodium acetate coupling occurs and the dyestui! separates as red brown precipitate. The latter is filtered with suction. washed with sodium chloride solution and poured into aqueous ammonia while stirring. The carminered solution is heated for 30 minutes to C. and acidified alter cooling with acetic acid. After the addition of sodium chloride the 2-diethylamino-iinaphthol-I-sulionic acid azophenyl-4'-sulionic acid amide separates as darki red'precipitate which is readily soluble in alkalies with brown red coloration.

Example 11.-32.4 grams of l-nitroso-Z-diethylamino-5-naphthol-7-sulionic acid (obtained by treating 2-diethylamino 5-naphthol-7-sulionic acid in concentrated hydrochloric acid with nitrous-acid) are dissolved in acetic acid and Example IL-20.8 grams of i-aminobensene sultonic acid diethylamide are diazotised in 111-" drochloric acid solution and coupled with 38.5 grams or the sodium salt orl-nahydroxyethy amino-8-naphthol-3fl-disuiionic 'acid in soda alkaline solution. The I-N-hydroXRtbyIaminoionicacid diethylamide formed is precipitated from the intensely red solutionby means of glacial acetic acid and sodium chloride in the form of a red readily soluble c powder.

when using instead of 4- nobenaene-sulionic acid diethylamide the d-aminobenaene suironic acid piperidide'or pyrro 'dide aso compounds of similar properties are tained.

Example 13.-17.2 grams of d-aminobenmnesulionic acid amide are dissolved in 25 cos. @of concentrated hydrochloric acid and: water and dlazotized with 6.9 grams of sodium nitrite. The

. diazo solution is mixed with a solution or 19.4

grams of d-acetamino-Z-amin'obensoir: acid in 15 cos. of concentrated hydrochloric acid. 20-

grams oi solid sodium acetate are gradually introduced while stirring. Thereby theW-sulionic acid amide-phenylazo-i -acetamino-2-amino- 'benzoic acid separates as a brown crystalline precipitate which is increased by the addition 0! sodium chloride solution. The dyestum which has been filtered with suction and pressed 0! is dissolved in dilutesodium carbonate solution and slightly acidified with dilute hydrochloric -8-naphthol-3,6-disulionic acid-azpphenyi-f-sulamass-1 v5 acid whereupon it is separated as an ocher yellow precipitate. It dissolves in causticsoda solution and sodiumcarbonatesolution with yellow coloration. It is slightly soluble in 30% acetic acid when cold, and dissolves with a yellow coloration when heated. Concentrated hydrochloric acid and concentrated sulfuric acid take up the dyestui! with a reddish brown coloration.

grams of the dyestufl are heated to boilin with 50 ccs..of hydrochloric acid (spec'. gravity 1.08) for half an hour while stirring. After coolsolution with a reddish yellow. in sodium car-- bonate solution with a brownish yellow coloration. It is only slightly soluble in acetic 5 acid when cold, when heated the dyestufi dissolves with reddish yellow coloration. Concen-.

trated hydrochloric acid takes up the dyestufi with a rose-red, concentrated sulfuric acid with brownish red coloration.

Example 14.-40.0 grams of d-aminobenzenesulfonic acld-dimethylamide are dissolved in cos. oi concentrated hydrochloric acid and water and diazotized with 13.8 grams of sodium nitrite. 33.4 grams of 3-aminophenoxy-acetic acid in 25 cos. of concentrated hydrochloric acid and water are added to the diazo solution and for completing the coupling crystallized sodium acetate is introduced while stirring. The 4'-sultonic acid 'dimethylamidephenylazo-3-amino-' phenoiwacetic acid separates in the form of orange colored crystals decomposing at 230 C. which dissolve in dilute sodium carbonate solution and caustic "soda solution with orange red coloration. With concentrated caustic soda solution the sodium salt is obtained from these solutions as a brownish precipitate.

stead of 40.0 grams of 4-aminobenzenesulfonic .para-position to the azo group and or disul ac'id-dimethvlamide 61.4 grams of aminoben zene-3,5-bi's(sultonic acid-dimethylamide) 'Ifhisis a continuation-in-part of our copending application Serial No. 15,696, nled April.

We claim: 1.-Azo compounds of the general formula:

wherein R stands for a cyclic radical selectedirom the group consisting of'radicals of the benzene series containlng'a sulfamide group in the famide substituted radicals of the benzene series and ofv the corresponding N-allryl and N-allrylene substituted products both' free valences of the alkylene radical being atom, which radicals are freefrom acid groups, p and wherein R. stands for acyclic radical 'conattached to the nitrogen cyclic radical by a member selected from the consisting of nuclear carbon atoms, oxygen atoms, amino-, alkylaminoand'allrylene groups,

which azo compounds are in the form or alkali and alkaline-earth metal-, and amine salts in general soluble in water. 2. Azo compounds of the general formula:

. RA-N=N-Ra wherein R standsiora benzene radical. which contains a sulfamide group inthe para-podiion" to the azo group and is free from acid groups, and wherein it. stands for a cyclic radical con taining nitrogen selected from the group consisting of aminobenzene and aminonaphthalene radicals and their N-acyl derivatives, which radicals contain at least one further substituent selected from the group consisting of amino, alkylamino and hydroxyl groups and fln'ther contain at least one acid radical which is bound tothe cyclic radical by a member selected from the grouplconsisting of nuclear carbonatoms, omgen atoms, amino-, alkylamino and alblene groups, which azo compounds are in the form of theiralkali and alkaline-earth -metal-, ammonium and amine saltsin general soluble in water. v 3. Azo compounds of the general formula:

wherein R stands tor a cyclic radical selected from the group consisting of radicals of the benzene series containing a sulfamide group in of the alkylene radical belngattached to the I nitrogen atom, which radicals are free from acid groups, and wherein R. stands for an amino- ,naphthalene radical (including the N-acylated radicals) which contains at least one further substituent selected from the group consisting of amino, alkylamino'andahydroxyl groups and iurther contains at least one acid radical which is bound to the aminon'aphthalene radical by a h u consistin of A similar dyestufl' is obtained when using inmember selected from t e gm p nuclear carbon atoms, oxygen atoms, amino-,

alkylarninoand alkylene groups, which azo compounds are in the form of their alkali and alkaline-earth metal-, ammoniumand amine salts in general soluble in water. 4. Azo compounds of the general formula:

wherein R stands for a benzene radical which contains a sulfamide group in the para-position to the azo group and is ireefrom acid groups.

and wherein R stands for an amino-naphthalene radical (including the N-acylated radicals) which contains at least one further substituent selected from the group consisting of. amino, alkylamino and hydroxyl groups and further contains at least one acid radical which is bound to the aminonaphthalene radical by a member selected from the group consisting of nuclear carbon atoms, oxygen atoms, 'amino-, alkylaminoand alkylene groups, which azo compounds are in the form of their alkaliand alkalineearth metal-, ammoniumand amine salts in general soluble in water.

5. Azo compounds of the general formula:

wherein R stands for a benzene radical which contains a suliamide group in the para-positionto the azo group and is free from acid groups, and R stands for an aminonaphthalene radical (including the N-acylated' radicals) substituted by a hydroxyl group and at least one sulio group,

which azo compounds are'in the form of their alkaliand alkaline-earth metal-, ammonium and amine salts in general-soluble in water.

6. Azo compounds of the general formula v 1 N'==NR wherein R stands for a cyclic radical selected from the group consisting of radicals of the henzene series containing a suliamide group in the para-position to the a'zo group andoi disuliamide substituted radicals of the benzene series which radicals are free from acid groups, and v wherein 1%. stands for a cyclic radical from the group consisting of radicals of the benzene series containing a sulfamide group in the para-position to the azo group and of disulfamide' substituted radicals ofthe benzene series which-are tree from acid groups, and R .stands for an aminophenol radical substituted by at least one acid, radical, which no compounds are in the form or their alkaliand alkaline-earth metal-, ammonium and amine salts in general soluble in water.

8. Azo compounds oi the general iormua:

- v NHl' B1-N=N wherein n stands for a benzene radical which contains a suliamide group in the-para-poation to the azo gro'upand is free from acid groups,

x which azo compounds are in the form. of their alkaliand alkaline-earth metal-, ammoniumand amine salts in general soluble in water. 9. Azo compounds of the general formula:

B1-N=N mu.

wherein R stands for a benzene radical which contains a sulfamide group in the para-position to the azo group and is free from acid groups. and g ac stands for an acyl group, whichaao compounds are in the form of their alkali and alkaline-earth metal-, ammonium and amine salts soluble in water.

10. The azo compound of the formula:

rim.o,s-ON=n maoocm soar K018 which is in the form or its alkali and alkalineearth metal, ammonium and amine salts soluble in water.

11. Ace compounds of the general formula:

wherein R 'stands for a benzene radical which contains a suliamide group in the para-position to the azo group'and is free from acid groups. and R stands for an aminobensene radical (including the N-acylated radicals) which contains at least 'one further substituent selected i'rom the group consisting of amino-, alblaininoland hydroxyl groups and iurther contains at least one carboxylic acid radical which is bound to the aminobenzene radical by a member selected from the group consisting of nuclear carbon atoms, oxygen atoms, amino-, and alkylene groups, which azo compounds are in the form or their alkali and alkaline-earth meta.l-, ammonium and amine salts soluble in water. v i

Joan-manna. 

